CN102952143A - Preparation method of tetraphenylporphin - Google Patents
Preparation method of tetraphenylporphin Download PDFInfo
- Publication number
- CN102952143A CN102952143A CN2012104444182A CN201210444418A CN102952143A CN 102952143 A CN102952143 A CN 102952143A CN 2012104444182 A CN2012104444182 A CN 2012104444182A CN 201210444418 A CN201210444418 A CN 201210444418A CN 102952143 A CN102952143 A CN 102952143A
- Authority
- CN
- China
- Prior art keywords
- pyrroles
- filter cake
- tetraphenylporphines
- preparation
- product
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- YNHJECZULSZAQK-UHFFFAOYSA-N tetraphenylporphyrin Chemical compound C1=CC(C(=C2C=CC(N2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3N2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 YNHJECZULSZAQK-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims abstract description 68
- 239000000047 product Substances 0.000 claims abstract description 54
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 49
- 230000003647 oxidation Effects 0.000 claims abstract description 47
- 238000006243 chemical reaction Methods 0.000 claims abstract description 46
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 44
- 239000012065 filter cake Substances 0.000 claims abstract description 38
- 235000019260 propionic acid Nutrition 0.000 claims abstract description 34
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims abstract description 34
- 239000002904 solvent Substances 0.000 claims abstract description 32
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000001301 oxygen Substances 0.000 claims abstract description 30
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 30
- 150000003934 aromatic aldehydes Chemical class 0.000 claims abstract description 25
- 239000000203 mixture Substances 0.000 claims abstract description 23
- 239000000706 filtrate Substances 0.000 claims abstract description 21
- 239000007789 gas Substances 0.000 claims abstract description 21
- 238000001914 filtration Methods 0.000 claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 4
- 150000003233 pyrroles Chemical class 0.000 claims description 78
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 238000010992 reflux Methods 0.000 claims description 8
- PKZJLOCLABXVMC-UHFFFAOYSA-N 2-Methoxybenzaldehyde Chemical compound COC1=CC=CC=C1C=O PKZJLOCLABXVMC-UHFFFAOYSA-N 0.000 claims description 6
- IAVREABSGIHHMO-UHFFFAOYSA-N 3-hydroxybenzaldehyde Chemical compound OC1=CC=CC(C=O)=C1 IAVREABSGIHHMO-UHFFFAOYSA-N 0.000 claims description 6
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 claims description 6
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 6
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 6
- -1 phenyl aldehyde Chemical class 0.000 claims description 6
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical compound CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 claims description 5
- FPYUJUBAXZAQNL-UHFFFAOYSA-N 2-chlorobenzaldehyde Chemical compound ClC1=CC=CC=C1C=O FPYUJUBAXZAQNL-UHFFFAOYSA-N 0.000 claims description 3
- ZWDVQMVZZYIAHO-UHFFFAOYSA-N 2-fluorobenzaldehyde Chemical compound FC1=CC=CC=C1C=O ZWDVQMVZZYIAHO-UHFFFAOYSA-N 0.000 claims description 3
- SRWILAKSARHZPR-UHFFFAOYSA-N 3-chlorobenzaldehyde Chemical compound ClC1=CC=CC(C=O)=C1 SRWILAKSARHZPR-UHFFFAOYSA-N 0.000 claims description 3
- WMPDAIZRQDCGFH-UHFFFAOYSA-N 3-methoxybenzaldehyde Chemical compound COC1=CC=CC(C=O)=C1 WMPDAIZRQDCGFH-UHFFFAOYSA-N 0.000 claims description 3
- AVPYQKSLYISFPO-UHFFFAOYSA-N 4-chlorobenzaldehyde Chemical compound ClC1=CC=C(C=O)C=C1 AVPYQKSLYISFPO-UHFFFAOYSA-N 0.000 claims description 3
- UOQXIWFBQSVDPP-UHFFFAOYSA-N 4-fluorobenzaldehyde Chemical compound FC1=CC=C(C=O)C=C1 UOQXIWFBQSVDPP-UHFFFAOYSA-N 0.000 claims description 3
- 235000014493 Crataegus Nutrition 0.000 claims description 3
- 241001092040 Crataegus Species 0.000 claims description 3
- BTFQKIATRPGRBS-UHFFFAOYSA-N o-tolualdehyde Chemical compound CC1=CC=CC=C1C=O BTFQKIATRPGRBS-UHFFFAOYSA-N 0.000 claims description 3
- ZRSNZINYAWTAHE-UHFFFAOYSA-N p-methoxybenzaldehyde Chemical compound COC1=CC=C(C=O)C=C1 ZRSNZINYAWTAHE-UHFFFAOYSA-N 0.000 claims description 3
- FXLOVSHXALFLKQ-UHFFFAOYSA-N p-tolualdehyde Chemical compound CC1=CC=C(C=O)C=C1 FXLOVSHXALFLKQ-UHFFFAOYSA-N 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 47
- 239000013067 intermediate product Substances 0.000 abstract description 23
- 238000000926 separation method Methods 0.000 abstract description 5
- 238000001816 cooling Methods 0.000 abstract description 4
- 238000000746 purification Methods 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 abstract 6
- AYEKOFBPNLCAJY-UHFFFAOYSA-O thiamine pyrophosphate Chemical compound CC1=C(CCOP(O)(=O)OP(O)(O)=O)SC=[N+]1CC1=CN=C(C)N=C1N AYEKOFBPNLCAJY-UHFFFAOYSA-O 0.000 description 68
- 239000000376 reactant Substances 0.000 description 25
- 239000007787 solid Substances 0.000 description 17
- 230000008569 process Effects 0.000 description 16
- 238000001291 vacuum drying Methods 0.000 description 15
- 239000007788 liquid Substances 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000012535 impurity Substances 0.000 description 9
- 239000002994 raw material Substances 0.000 description 6
- 230000035484 reaction time Effects 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 230000001590 oxidative effect Effects 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- 239000000498 cooling water Substances 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 239000012530 fluid Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 150000004032 porphyrins Chemical class 0.000 description 3
- 239000012265 solid product Substances 0.000 description 3
- 238000010189 synthetic method Methods 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 210000003298 dental enamel Anatomy 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 238000010907 mechanical stirring Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- NUOYJPPISCCYDH-BYPYZUCNSA-N (2s)-1-(2,2,2-trifluoroacetyl)pyrrolidine-2-carbonyl chloride Chemical compound FC(F)(F)C(=O)N1CCC[C@H]1C(Cl)=O NUOYJPPISCCYDH-BYPYZUCNSA-N 0.000 description 1
- AQZMINLSVARCSL-UHFFFAOYSA-N 4-chloro-3,6-dioxocyclohexa-1,4-diene-1,2-dicarbonitrile Chemical class ClC1=CC(=O)C(C#N)=C(C#N)C1=O AQZMINLSVARCSL-UHFFFAOYSA-N 0.000 description 1
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229960001701 chloroform Drugs 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910001867 inorganic solvent Inorganic materials 0.000 description 1
- 239000003049 inorganic solvent Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Landscapes
- Pyrrole Compounds (AREA)
Abstract
The invention discloses a preparation method of tetraphenylporphin. The preparation method comprises the following steps of: (1) adding a solvent, aromatic aldehyde and pyrrole into a polymerization reactor and then heating until the mixture reflows, wherein the molar ratio of the aromatic aldehyde to the pyrrole is 1-2:1; keeping molar concentration of the pyrrole in the reaction system at 0.1-0.4 mol/L; reflowing for 0.2-0.5 hour and then stopping heating; cooling to normal temperature; filtering to obtain filtrate and filter cake; adding the filter cake and propionic acid obtained by the step (1) into an oxidation reactor and heating until the mixture reflows; introducing oxygen-containing gas to oxidize for 0.3-1 hour, wherein the mass ratio of the filter cake to the propionic acid is 0.5-3:100; cooling and filtering to obtain filter cake and filtrate after the oxidation is finished; and washing, centrifuging and drying the filter cake to obtain a tetraphenylporphin product. The method has the advantages of high yield, safety, environmental friendliness, simple separation and purification, stable product quality, maximum yield of the tetraphenylporphin of 37.3 percent and capabilities of reducing the content of intermediate product dihydrotetraphenylporphin to be below 0.9 percent and reaching product purity of over 98 percent.
Description
Technical field
The present invention relates to a kind of preparation method of porphines, be specifically related to a kind of method for preparing tetraphenylporphines with pyrroles, aromatic aldehyde and oxygen-containing gas.
Background technology
Tetraphenylporphines (hereinafter to be referred as TPP) is important luminescent material, also is the raw material of synthetic metalloporphyrin.The Adler method is the best way of the synthetic tetraphenylporphines of generally acknowledging, and it is reaction raw materials that this method adopts pyrroles and phenyl aldehyde, synthetic TPP (J.Am.Chem.Soc., 1964,86:3145 of reaction in the backflow propionic acid; J.Org.Chem., 1967,32:476).But this method obtain in pyrroles's TPP yield less than 20%, and wherein contain 5 ~ 10% impurity dihydro tetraphenylporphines (hereinafter to be referred as TPC).In order to remove the TPC impurity that is mixed with among the TPP, investigator has afterwards carried out a large amount of improvement to the Adler method, mainly concentrate on both direction: the TPP that (1) will contain TPC impurity is dissolved in the organic solvents such as benzene, dimethyl sulfoxide (DMSO), methylene dichloride, trichloromethane, and the method that then adopts chromatographic column to separate is removed TPC.After the TPP that (2) will contain TPC impurity is dissolved in certain organic solvent, add a certain amount of reduction oxygenant such as TCBQ, 2,3-two chloro-5,6-dicyanobenzoquinones etc. are oxidized to TPC TPP and remove TPC.Because TPP and the TPC solubleness in organic and inorganic solvent is all very little, no matter be chromatogram column technique or adding chemical oxidation agent method, all need to increase the separation of a large amount of solvents; operation is many; solvent loss is large, and production cost is high, is not suitable for industrial large-scale production.And; these methods are all considered the composition problem of TPP from the angle of how purifying; and the rare composition problem of considering TPP from the angle that improves reaction yield; cause in the yield of pyrroles's TPP lower; and the pyrroles is expensive; be cost factor important when producing TPP, this also causes existing synthetic method production cost high, is not suitable for industrial large-scale production.
China Patent Publication No. CN101550140A, open day on October 7th, 2009, denomination of invention: the synthetic method of tetaraary porphyrin and equipment.It is the method for the synthetic tetaraary porphyrin of raw material high yield (being called for short TAP) by pyrroles, aromatic aldehyde and air that this application case discloses a kind of.This synthetic method relates to be finished simultaneously the pyrroles polycondensation becomes two reactions of atmospheric oxidation of dihydro tetaraary porphyrin (be called for short TAC) and TAC with aromatic aldehyde in same reactor.This method lays particular emphasis on the purification of TAP equally, has proposed directly oxygen containing air to be passed in the polymerization oxidation reactor to react, and part TAC is oxidized to TAP, thereby reaches the effect of purification TAP.But this method adopts and directly air is passed in the polymerization reactor, when oxidation TAC becomes TAP, also complete pyrroles and the aromatic aldehyde of unreacted in the oxidized system, the Direct Loss that not only cause important reaction raw materials pyrroles, synthetic yield reduces, raised the TAP production cost, sneaked in the product after also having caused a large amount of aromatic aldehydes to be oxidized to aromatic acid, so that the follow-up crystallization of product is filtered and washing purification process difficult.And, after pyrroles and the air mixed, easily producing volatile gas, the safety problem during industrial production is not mentioned in this patent yet.
Summary of the invention
Technical problem to be solved by this invention provides that a kind of yield is high, safety and environmental protection, separating-purifying are simple, the preparation method of the tetraphenylporphines of constant product quality.
The present invention solves the problems of the technologies described above the technical scheme that adopts: a kind of preparation method of tetraphenylporphines may further comprise the steps:
(1) in polymerization reactor, adds solvent, aromatic aldehyde and pyrroles's post-heating to refluxing, aromatic aldehyde and pyrroles's mol ratio is 1 ~ 2:1, the volumetric molar concentration that makes pyrroles in the reaction system is 0.1 ~ 0.4mol/L, stopped heating after 0.2 ~ 0.5 hour refluxes, be cooled to normal temperature, filter and obtain filtrate and filter cake;
(2) after being heated to backflow in the filter cake that step (1) is obtained and the propionic acid adding oxidation reactor, pass into oxygen-containing gas and carry out oxidation, oxidization time is 0.3～1 hour, described filter cake and propionic acid mass ratio are 0.5 ~ 3:100, cool off, filter and to get filter cake and filtrate after oxidation finishes, with filter cake washing, centrifugal, be drying to obtain the tetraphenylporphines product.
Aromatic aldehyde structural formula described in the step (1) is as follows:
Wherein, substituent R
1, R
2, R
3Be selected from respectively a kind of in hydrogen, alkyl, alkoxyl group, hydroxyl or the halogen.
Aromatic aldehyde described in the step (1) is selected from a kind of in phenyl aldehyde, 4-chloro-benzaldehyde, p-Fluorobenzenecarboxaldehyde, o-chlorobenzaldehyde, o fluorobenzaldehyde, o-tolualdehyde, p-tolyl aldehyde, o-methoxybenzaldehyde, aubepine, salicylaldhyde, p-Hydroxybenzaldehyde, m chlorobenzaldehyde, m-hydroxybenzaldehyde, the NSC 43794.
Solvent described in the step (1) is selected from the mixture of a kind of composition in propionic acid or propionic acid and benzene, toluene, p-Xylol, the hexanaphthene.
The quality percentage composition of oxygen is 10 ~ 100% in the oxygen-containing gas described in the step (2).
Oxygen-containing gas described in the step (2) is pure oxygen, oxygen-rich air, airborne a kind of.
Recycle in the adding polymerization reactor after removing water treatment filtering the filtrate that obtains in the step (1).
Recycle filtering the direct adding of the filtrate that obtains in the step (2) or after removing water treatment, adding in the oxidation reactor.
Find through experiment, under the condition that oxygen-containing gas exists, pyrroles and aromatic aldehyde polyreaction generate the reaction of tetraphenylporphines carries out in two steps, such as reaction equation (a) with (b):
In reaction (a), reactant pyrroles B and aromatic aldehyde A occur each other four and gather, and form intermediate product dihydro tetraphenylporphines C (hereinafter to be referred as TPC) and water.In reaction (b), intermediate product TPC is oxidized to target product tetraphenylporphines D (hereinafter to be referred as TPP) under the effect of oxygen.TPC is the major impurity among the TPP.
Pyrroles's autohemagglutination has considerable influence to product yield, and the contriver finds, the concentration by the control pyrroles can reduce the speed of pyrroles's autohemagglutination a lower scope.Simultaneously, by suitable increasing reactant aromatic aldehyde and pyrroles's concentration ratio, can be so that pyrroles's conversion be more complete.Therefore, in the present invention, raw material aromatic aldehyde and pyrroles's molar ratio are controlled to be 1 ~ 2:1, and the volumetric molar concentration that polyreaction begins pyrroles in the front reaction system is controlled at 0.1 ~ 0.4mol/L.
Reaction times is the important factor that affects product yield.To reaction (a), experimental result reflects that this reaction kinetics is close to secondary, to reactant pyrroles and aromatic aldehyde concentration all near one-level.Very slow reaction later stage pyrroles and the density loss of aromatic aldehyde in system, after reaction for some time, continue to prolong the reaction times little to the yield raising of reaction product.And under temperature of reaction, autohemagglutination also can occur in pyrroles self, and the prolongation in reaction times can add the autohemagglutination of polypyrrole.The contriver finds after deliberation, pyrroles and aromatic aldehyde speed of response are very fast, the growing amount of intermediate product TPC has namely reached stable rear more than 75% of growing amount about 10 minutes, the growing amount of intermediate product TPC has namely reached stable rear more than 90% of growing amount about 30 minutes, increase again the reaction times, generation to middle product TPC is not obvious, on the contrary, under the effect of high temperature, reactant pyrroles's autohemagglutination is serious, and the prolongation reaction times only can be aggravated reactant pyrroles's autohemagglutination, reduces the yield in reactant pyrroles's TPC, owing to autohemagglutination generates a large amount of black polymers, cause follow-up TPP separating-purifying difficulty simultaneously.The method of conventional synthetic TPP all is to react more than 0.5 hour, and the yield that this not only can not increase product also can produce a large amount of polymeric by-products, causes follow-up sepn process difficulty.And the time that the inventor is undertaken by control reaction (a) is adjusted the concentration of pyrroles in the reaction solution, can effectively reduce pyrroles's autohemagglutination, and therefore, the time that reaction (a) is carried out among the present invention is controlled at 0.2 ~ 0.5 hour.
Solvent has certain impact to aromatic aldehyde and pyrroles's polyreaction.Solvent among the present invention can be selected the mixture of a kind of composition in propionic acid or propionic acid and benzene, toluene, p-Xylol, the hexanaphthene.The effect that adds benzene, toluene, p-Xylol or hexanaphthene in the solvent propionic acid has been the effect of band aqua, takes the water that generates in the reaction system out of reaction system by the evaporation of solvent, in order to avoid cause temperature of reaction to descend because water concentration is too high, affects speed of response.
According to the present invention, before polymerization reactor begins to heat up, need use N
2With the O in the reactor
2Replace to tail oxygen concentration below 3%, so as not to after the pyrroles be evaporated in the temperature-rise period and air form volatile gas-phase space.Then begin to heat up, begin timing when occurring refluxing from being warming up to, polymerization reaction time is 0.2 ~ 0.5 hour.Then being cooled to the method that adopts conventional separation method such as crystallization to filter behind the normal temperature shifts out solid product from reaction solution, the main component of solid product is intermediate product TPC, be mixed with simultaneously the target product TPP that partly is dissolved in the dioxygen oxidation in the solvent and generates, therefore solid product is the mixture of TPC and TPP, is called thick TPP among the present invention.Outside desolventizing in the filtrate that filtration obtains, also be mixed with water byproduct, a small amount of unreacted is pyrroles and aromatic aldehyde and pyrroles's autohemagglutination product and undecomposed TPC and TPP completely.The pyrroles is the high raw material of added value, need reclaim.The large usage quantity of solvent also need recycle and reuse.By conventional lock out operation such as distillation operation, can be with unreacted in the filtrate completely pyrroles and solvent recuperation, the pyrroles who returns and solvent can again loop back and participate in reaction in the polymerization reactor, outside the water byproduct of reaction and the distillation residue discharge system, and otherwise processed.
Oxidation time is larger on the impact of product yield.To the reaction (b), experimental result reflects that this reaction kinetics is close to one-level to reactant TPC, to reactant oxygen near zero level.By prolonging the concentration of the time energy impurity reduction TPC that leads to oxygen, improve the purity of TPP.But experiment is found, leads under the oxygen condition at high temperature, and TPP also can be oxidized by oxygen and degrade, and reduces the yield of TPP.The time of being undertaken by control reaction (b) is adjusted the concentration of TPC in the reaction solution, controls simultaneously the degraded of TPP, can not lose the yield of TPP when improving TPP purity as far as possible.Therefore, the time that reaction (b) is carried out among the present invention is controlled at 0.3 ~ 1 hour.
During oxidizing reaction, pass into oxygen-containing gas after need again being dissolved in the solvent propionic acid by the thick TPP filter cake that obtains in the polyreaction and carry out oxidizing reaction, described filter cake and propionic acid mass ratio are 0.5 ~ 3:100.Temperature of reaction is the boiling point of system, and reaction pressure is normal pressure, in the reaction process constantly stirring reaction liquid with fast reaction speed.The quality percentage composition of oxygen is 10% ~ 100% in the oxygen-containing gas among the present invention., preferred pure oxygen, oxygen-rich air, airborne a kind of.
According to the present invention, oxidation time is 0.3 ~ 1 hour, and stopped heating after oxidizing reaction finishes stops ventilation, and is cooled to normal temperature, and the product TPP that generates in the reaction system can crystallization.Adopt conventional separation method as filtering or centrifugal method, the mixture of TPP is separated from system.The TPP that this step obtains is the crude product of target product, a small amount of intermediate product TPC and a small amount of pyrroles's polymkeric substance are still contained in the inside, aromatic aldehyde oxidation productss etc. can use conventional method to purify, for example with after the hot wash again with methyl alcohol or washing with alcohol filter cake.Desolventize outside the propionic acid in the filtrate that filtration obtains, also be mixed with water byproduct, a small amount of undecomposed TPC and TPP and the polymeric impurities of being come by the filter cake band.The large usage quantity of solvent propionic acid need recycle and reuse, and by conventional lock out operation such as distillation operation, the solvent propionic acid can be reclaimed, and the propionic acid of returning can again loop back and participate in reaction in the oxidation reactor.But simultaneously, because the impurity concentration in the filtrate is lower, be mixed with simultaneously saturated TPC and TPP.In order to reduce the loss of TPP, reduce simultaneously separating energy consumption, the filtrate that filtration can be obtained is without any processing, carry out again conventional lock out operation such as distillation operation after direct repeat utilizes 2 ~ 5 times and reclaim the solvent propionic acid, then again loop back sustainable participation reaction in the oxidation reactor, outside the water byproduct and residue discharge system of reaction, otherwise processed.
According to the present invention, TPP and TPC content liquid-phase chromatographic analysis in the product.Because the pyrroles is the most expensive reactant of price in this reaction, its autohemagglutination or oxidation products also are the most difficult impurity of removing among the TPP, therefore, among the present invention in the synthetic yield of pyrroles's TPP as one of item key of weighing the technological process quality, method of calculation are:
The present invention has the following advantages:
1, yield is high, is up to 37.3% in the synthetic yield of reactant pyrroles's tetraphenylporphines, below the content to 0.9% of intermediate product dihydro tetraphenylporphines;
2, operational safety, product separation is purified simple, and after the employing ordinary method was processed, product purity reached more than 98%, is fit to commercial scale production;
3, three waste discharge is few, the filtrate reusable edible.
Description of drawings
Fig. 1 is craft block-diagram of the present invention.
As shown in the figure:
Wherein A is phenyl aldehyde, and B is that pyrroles, E are solvent, and D is the target product tetraphenylporphines;
1 is polymerization reactor, and 2 is the filtration washing device, and 3 is the polymerization solvent rectifying tower, and 4 is oxidation reactor, and 5 is the filtration washing device, and 6 is the oxidation solvent rectifying tower, and 7 is drying installation.
Embodiment
Below in conjunction with drawings and Examples the present invention is described in further detail, but the present invention is not limited to described embodiment.
Embodiment 1
At the 5m with mechanical stirring and chuck, still heading tape condensing reflux
3In the enamel polymerization reactor, add 3.5m
3Then the solvent propionic acid adds 1400mol pyrroles and 1400mol phenyl aldehyde, and blasts N from the polymerization reactor bottom
2Oxygen concn is lower than 3% to the gas phase of reactor top condensator outlet, then in the polymerization reactor chuck, pass into middle pressure steam to reactor in liquid be heated to backflow, stopped heating behind the backflow 15min.Middle pressure steam in the chuck is switched to recirculated cooling water cool off, in being cooled to polymerization reactor, stop to pass into recirculated cooling water during 90 ℃ of left and right sides of fluid temperature, and change by naturally cooling.After fluid temperature is down to normal temperature in the polymerization reactor with polymerization reactor in liquid be delivered in the deep bed filter to filter and obtain filtrate and the higher filter cake of moisture percentage, then this filter cake is further carried out centrifugal filtrate and the thick TPP filter cake 86.6kg of obtaining.The filtrate that deep bed filter and centrifugal filter obtain pumps into tower reactor volume 5m
3, with rectifying in the polymerization solvent rectifying tower of 3 joint DN400*1000 towers joints, dehydration and reclaim obtains completely pyrroles of solvent propionic acid and unreacted, continue to use in order to looping back polymerization reactor after the propionic acid that reclaims and pyrroles collected, outside the residue discharge system of rectifying tower reactor, otherwise processed.
The thick TPP filter cake 86.6kg that centrifuging is obtained adds one with mechanical stirring and chuck, top band condensing reflux, the bottom 5m with gas distributor
3The enamel oxidation reactor in, add simultaneously the 3500kg propionic acid in the still, then in reacting kettle jacketing, pass into middle pressure steam liquid in the oxidation reactor heated.After liquid heat in the oxidation reactor extremely refluxes, pass into air and carry out oxidizing reaction, oxidation time is 22 minutes.After oxidizing reaction finishes, the middle pressure steam in the oxidation reactor chuck is switched to recirculated cooling water cool off, in being cooled to reactor, stop to pass into recirculated cooling water during 90 ℃ of left and right sides of fluid temperature, and change by naturally cooling.After fluid temperature is down to normal temperature in the oxidation reactor with oxidation reactor in liquid be delivered in the deep bed filter and filter, then the filter cake that obtains in the deep bed filter is carried out centrifuging.The filtrate that deep bed filter and centrifugal filter obtain can pump into tower reactor volume 5m
3, with rectifying in the oxidation solvent rectifying tower of 3 joint DN400*1000 towers joints, dehydration is also reclaimed and is obtained the solvent propionic acid, continues to use in order to looping back oxidation reactor after the propionic acid that will reclaim is collected, outside the residue discharge system of rectifying tower reactor.The filtrate that deep bed filter and centrifugal filter obtain also can be without any processing, and direct circulation returns oxidation reactor to be continued to use.
The solid that centrifugal filter is obtained is repeatedly with centrifuging after the hot wash, until the waste water that centrifuging obtains is substantially colourless.Then the solid that centrifuging is obtained filters with recentrifuge after the methanol wash more repeatedly, until the waste water that centrifuging obtains is substantially colourless.The solid of crossing through methanol wash is product TPP, obtains tetraphenylporphines product 77.1kg after 80 ℃ of vacuum-drying, take the synthetic yield of reactant pyrroles's product TPP as 35.9%, and purity 98.3%, the content of intermediate product TPC is 0.9%.
Embodiment 2
Technical process is identical with embodiment 1, and difference is:
(1) in polymerization reactor, adds 1225mol pyrroles and 1400mol phenyl aldehyde;
(2) quality of thick TPP filter cake is 73.4kg;
Solid after the washing obtains product TPP63.9kg after 80 ℃ of vacuum-drying, take the synthetic yield of reactant pyrroles's product TPP as 33.9%, and purity 98.0%, the content of intermediate product TPC is 0.9%.
Embodiment 3
Technical process is identical with embodiment 1, and difference is:
(1) in polymerization reactor, adds 350mol pyrroles and 700mol 4-chloro-benzaldehyde;
(2) solvent that adds in the polymerization reactor is the mixture of propionic acid and hexanaphthene;
(3) the liquid return time is 12 minutes in the polymerization reactor;
(4) gas that passes in the oxidation reactor is pure oxygen, oxidation time 18 minutes;
(5) thick TPP filter cake is 20.1kg;
By this method, the solid that obtains at last obtains product TPP17.2kg after 80 ℃ of vacuum-drying, take the synthetic yield of reactant pyrroles's product TPP as 26.2%, and purity 98.9%, the content of intermediate product TPC is 0.7%.
Embodiment 4
Technical process is identical with embodiment 1, and difference is:
(1) in polymerization reactor, adds 350mol pyrroles and 700mol o-chlorobenzaldehyde;
(2) solvent that adds in the polymerization reactor is the mixture of propionic acid and toluene;
(3) the liquid return time is 18 minutes in the polymerization reactor;
(4) gas that passes in the oxidation reactor is by N
2The mixed gas of the oxygen quality percentage composition 10% that is made into pure oxygen, oxidation time 60 minutes;
(5) thick TPP filter cake is 20.5kg;
By this method, the solid that obtains at last obtains product TPP17.4kg after 80 ℃ of vacuum-drying, take the synthetic yield of reactant pyrroles's product TPP as 26.3%, and purity 98.6%, the content of intermediate product TPC is 0.8%.
Embodiment 5
Technical process is identical with embodiment 1, and difference is:
(1) in polymerization reactor, adds 386mol pyrroles and 400mol o-tolualdehyde;
(2) solvent that adds in the polymerization reactor is the mixture of propionic acid and benzene;
(3) the liquid return time is 30 minutes in the polymerization reactor;
(4) gas that passes in the oxidation reactor is that the oxygen quality percentage composition is 50% oxygen-rich air, oxidation time 45 minutes;
(5) thick TPP filter cake is 23.2kg;
By this method, the solid that obtains at last obtains product TPP20.2kg after 80 ℃ of vacuum-drying, take the synthetic yield of reactant pyrroles's product TPP as 31.2%, and purity 98.6%, the content of intermediate product TPC is 0.8%.
Embodiment 6
Technical process is identical with embodiment 1, and difference is:
(1) in polymerization reactor, adds 386mol pyrroles and 400mol p-tolyl aldehyde;
(2) gas that passes in the oxidation reactor is that the oxygen quality percentage composition is 75% oxygen-rich air, oxidation time 18 minutes;
(3) thick TPP filter cake is 23.5kg;
By this method, the solid that obtains at last obtains product TPP20.4kg after 80 ℃ of vacuum-drying, take the synthetic yield of reactant pyrroles's product TPP as 31.6%, and purity 98.4%, the content of intermediate product TPC is 0.9%.
Embodiment 7
Technical process is identical with embodiment 1, and difference is:
(1) in polymerization reactor, adds 1225mol pyrroles and 1225mol salicylaldhyde;
(2) solvent that adds in the polymerization reactor is the mixture of propionic acid and p-Xylol;
(3) thick TPP filter cake is 75.2kg;
By this method, the solid that obtains at last obtains product TPP65.4kg after 80 ℃ of vacuum-drying, take the synthetic yield of reactant pyrroles's product TPP as 31.5%, and purity 98.6%, the content of intermediate product TPC is 0.8%.
Embodiment 8
Technical process is identical with embodiment 1, and difference is:
(1) in polymerization reactor, adds 1225mol pyrroles and 1225mol p-Hydroxybenzaldehyde;
(3) thick TPP filter cake is 74.9kg;
By this method, the solid that obtains at last obtains product TPP65.2kg after 80 ℃ of vacuum-drying, take the synthetic yield of reactant pyrroles's product TPP as 31.4%, and purity 98.6%, the content of intermediate product TPC is 0.8%.
Embodiment 9
Technical process is identical with embodiment 1, and difference is:
(1) in polymerization reactor, adds 1025mol pyrroles and 1225mol aubepine;
(2) solvent that adds in the polymerization reactor is the mixture of propionic acid and hexanaphthene;
(3) the liquid return time is 30 minutes in the polymerization reactor;
(4) gas that passes in the oxidation reactor is air, oxidation time 60 minutes;
(5) thick TPP filter cake is 80.2kg;
By this method, the solid that obtains at last obtains product TPP69.6kg after 80 ℃ of vacuum-drying, take the synthetic yield of reactant pyrroles's product TPP as 37.0%, and purity 98.2%, the content of intermediate product TPC is 0.9%.
Embodiment 10
Technical process is identical with embodiment 1, and difference is:
(1) in polymerization reactor, adds 1025mol pyrroles and 1225mol o-methoxybenzaldehyde;
(2) thick TPP filter cake is 80.4kg;
By this method, the solid that obtains at last obtains product TPP70.2kg after 80 ℃ of vacuum-drying, take the synthetic yield of reactant pyrroles's product TPP as 37.3%, and purity 98.0%, the content of intermediate product TPC is 0.9%.
Embodiment 11
Technical process is identical with embodiment 1, and difference is:
(1) in polymerization reactor, adds 1025mol pyrroles and 1225mol p-Fluorobenzenecarboxaldehyde;
(2) the liquid return time is 30 minutes in the polymerization reactor;
(3) gas that passes in the oxidation reactor is air, oxidation time 60 minutes;
(4) thick TPP filter cake is 65.7kg;
By this method, the solid that obtains at last obtains product TPP57.2kg after 80 ℃ of vacuum-drying, take the synthetic yield of reactant pyrroles's product TPP as 32.3%, and purity 99.1%, the content of intermediate product TPC is 0.6%.
Embodiment 12
Technical process is identical with embodiment 1, and difference is:
(1) in polymerization reactor, adds 1025mol pyrroles and 1225mol o fluorobenzaldehyde;
(2) thick TPP filter cake is 67.1kg;
By this method, the solid that obtains at last obtains product TPP58.4kg after 80 ℃ of vacuum-drying, take the synthetic yield of reactant pyrroles's product TPP as 33.0%, and purity 98.9%, the content of intermediate product TPC is 0.7%.
Embodiment 13
Technical process is identical with embodiment 1, and difference is:
(1) in polymerization reactor, adds 1300mol pyrroles and 1400mol m chlorobenzaldehyde;
The quality of the propionic acid that (2) adds in the oxidation reactor is 3200kg;
(3) thick TPP filter cake is 95.3kg;
By this method, the solid that obtains at last obtains product TPP82.9kg after 80 ℃ of vacuum-drying, take the synthetic yield of reactant pyrroles's product TPP as 34.1%, and purity 98.4%, the content of intermediate product TPC is 0.9%.
Embodiment 14
Technical process is identical with embodiment 1, and difference is:
(1) in polymerization reactor, adds 1225mol pyrroles and 1400mol m-hydroxybenzaldehyde;
The quality of the propionic acid that (2) adds in the oxidation reactor is 3200kg;
(3) thick TPP filter cake is 76.6kg;
By this method, the solid that obtains at last obtains product TPP66.7kg after 80 ℃ of vacuum-drying, take the synthetic yield of reactant pyrroles's product TPP as 32.1%, and purity 98.9%, the content of intermediate product TPC is 0.6%.
Embodiment 15
Technical process is identical with embodiment 1, and difference is:
(1) in polymerization reactor, adds 600mol pyrroles and 700mol NSC 43794;
(2) thick TPP filter cake is 46.3kg;
By this method, the solid that obtains at last obtains product TPP40.3kg after 80 ℃ of vacuum-drying, take the synthetic yield of reactant pyrroles's product TPP as 36.6%, and purity 98.2%, the content of intermediate product TPC is 0.8%.
Claims (8)
1. the preparation method of a tetraphenylporphines is characterized in that, may further comprise the steps:
(1) in polymerization reactor, adds solvent, aromatic aldehyde and pyrroles's post-heating to refluxing, aromatic aldehyde and pyrroles's mol ratio is 1 ~ 2:1, the volumetric molar concentration that makes pyrroles in the reaction system is 0.1 ~ 0.4mol/L, stopped heating after 0.2 ~ 0.5 hour refluxes, be cooled to normal temperature, filter and obtain filtrate and filter cake;
(2) after being heated to backflow in the filter cake that step (1) is obtained and the propionic acid adding oxidation reactor, pass into oxygen-containing gas and carry out oxidation, oxidization time is 0.3 ~ 1 hour, described filter cake and propionic acid mass ratio are 0.5 ~ 3:100, cool off, filter and to get filter cake and filtrate after oxidation finishes, with filter cake washing, centrifugal, be drying to obtain the tetraphenylporphines product.
2. the preparation method of tetraphenylporphines according to claim 1 is characterized in that, the aromatic aldehyde structural formula described in the step (1) is as follows:
Wherein, substituent R
1, R
2, R
3Be selected from respectively a kind of in hydrogen, alkyl, alkoxyl group, hydroxyl or the halogen.
3. the preparation method of tetraphenylporphines according to claim 2, it is characterized in that, the aromatic aldehyde described in the step (1) is selected from a kind of in phenyl aldehyde, 4-chloro-benzaldehyde, p-Fluorobenzenecarboxaldehyde, o-chlorobenzaldehyde, o fluorobenzaldehyde, o-tolualdehyde, p-tolyl aldehyde, o-methoxybenzaldehyde, aubepine, salicylaldhyde, p-Hydroxybenzaldehyde, m chlorobenzaldehyde, m-hydroxybenzaldehyde, the NSC 43794.
4. the preparation method of tetraphenylporphines according to claim 1 is characterized in that, the solvent described in the step (1) is selected from the mixture of a kind of composition in propionic acid or propionic acid and benzene, toluene, p-Xylol, the hexanaphthene.
5. the preparation method of tetraphenylporphines according to claim 1 is characterized in that, the quality percentage composition of oxygen is 10 ~ 100% in the oxygen-containing gas described in the step (2).
6. the preparation method of tetraphenylporphines according to claim 5 is characterized in that, the oxygen-containing gas described in the step (2) is pure oxygen, oxygen-rich air, airborne a kind of.
7. the preparation method of tetraphenylporphines according to claim 1 is characterized in that, recycles in the adding polymerization reactor after removing water treatment filtering the filtrate that obtains in the step (1).
8. the preparation method of tetraphenylporphines according to claim 1 is characterized in that, recycles filtering the direct adding of the filtrate that obtains in the step (2) or adding in the oxidation reactor after removing water treatment.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210444418.2A CN102952143B (en) | 2012-11-08 | 2012-11-08 | A kind of preparation method of tetraphenylporphines |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210444418.2A CN102952143B (en) | 2012-11-08 | 2012-11-08 | A kind of preparation method of tetraphenylporphines |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102952143A true CN102952143A (en) | 2013-03-06 |
| CN102952143B CN102952143B (en) | 2015-12-02 |
Family
ID=47761581
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210444418.2A Expired - Fee Related CN102952143B (en) | 2012-11-08 | 2012-11-08 | A kind of preparation method of tetraphenylporphines |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102952143B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105085536A (en) * | 2015-09-17 | 2015-11-25 | 唐江涛 | Preparation method of meso-tetraphenylchlorin |
| CN105198890A (en) * | 2015-09-17 | 2015-12-30 | 唐江涛 | Production method for tetraphenyl porphin |
| CN105646504A (en) * | 2016-01-15 | 2016-06-08 | 唐江涛 | Method for continuously preparing tetraphenyl porphin |
| CN109824679A (en) * | 2019-04-08 | 2019-05-31 | 中国科学院长春应用化学研究所 | A kind of preparation method of substituted aryl porphyrin |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1549729A (en) * | 2001-08-30 | 2004-11-24 | Pci���＼����˾ | Compound |
| CN101050218A (en) * | 2007-05-11 | 2007-10-10 | 北京工业大学 | Method for synthesizing MU - oxygen substitutional binuclear metalloporphyrin |
| CN101070323A (en) * | 2006-05-13 | 2007-11-14 | 济南赛文医药技术有限公司 | Porphyrin derivative, its preparing method and use of same as small-molecular anti-oxidation agent |
| CN101550140A (en) * | 2009-05-15 | 2009-10-07 | 湖南大学 | Method and apparatus for synthesis of tetaraary porphyrin |
| CN101606933A (en) * | 2009-07-14 | 2009-12-23 | 东华大学 | Chlorin photosensitizer and its preparation and application |
| CN101759701A (en) * | 2008-12-11 | 2010-06-30 | 湖州来色生物基因工程有限公司 | Preparation method of novel porphyrin |
| CN102068428A (en) * | 2010-12-29 | 2011-05-25 | 东华大学 | Dihydroporphin photosensitizer and preparation and application thereof |
| CN102558187A (en) * | 2011-12-29 | 2012-07-11 | 东华大学 | Tetrahydroporphin compound and preparation method and application thereof |
-
2012
- 2012-11-08 CN CN201210444418.2A patent/CN102952143B/en not_active Expired - Fee Related
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1549729A (en) * | 2001-08-30 | 2004-11-24 | Pci���＼����˾ | Compound |
| CN101070323A (en) * | 2006-05-13 | 2007-11-14 | 济南赛文医药技术有限公司 | Porphyrin derivative, its preparing method and use of same as small-molecular anti-oxidation agent |
| CN101050218A (en) * | 2007-05-11 | 2007-10-10 | 北京工业大学 | Method for synthesizing MU - oxygen substitutional binuclear metalloporphyrin |
| CN101759701A (en) * | 2008-12-11 | 2010-06-30 | 湖州来色生物基因工程有限公司 | Preparation method of novel porphyrin |
| CN101550140A (en) * | 2009-05-15 | 2009-10-07 | 湖南大学 | Method and apparatus for synthesis of tetaraary porphyrin |
| CN101606933A (en) * | 2009-07-14 | 2009-12-23 | 东华大学 | Chlorin photosensitizer and its preparation and application |
| CN102068428A (en) * | 2010-12-29 | 2011-05-25 | 东华大学 | Dihydroporphin photosensitizer and preparation and application thereof |
| CN102558187A (en) * | 2011-12-29 | 2012-07-11 | 东华大学 | Tetrahydroporphin compound and preparation method and application thereof |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105085536A (en) * | 2015-09-17 | 2015-11-25 | 唐江涛 | Preparation method of meso-tetraphenylchlorin |
| CN105198890A (en) * | 2015-09-17 | 2015-12-30 | 唐江涛 | Production method for tetraphenyl porphin |
| CN105646504A (en) * | 2016-01-15 | 2016-06-08 | 唐江涛 | Method for continuously preparing tetraphenyl porphin |
| CN105646504B (en) * | 2016-01-15 | 2018-03-27 | 唐江涛 | A kind of continuous preparation method of tetraphenylporphines |
| CN109824679A (en) * | 2019-04-08 | 2019-05-31 | 中国科学院长春应用化学研究所 | A kind of preparation method of substituted aryl porphyrin |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102952143B (en) | 2015-12-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102020555B (en) | Method for preparing hindered phenol antioxygens by ester exchange process | |
| CN101648907B (en) | Purifying method of 2-chloromethyl-4-methoxyl-3,5-dimethylpyridine chloride | |
| KR102364274B1 (en) | Continuous process for the preparation of 2-methylallyl alcohol | |
| CN102775364B (en) | Preparation method of cross linking agent triallyl isocyanurate | |
| CN102417498A (en) | Synthetic method of 3- (alpha-methoxy) methylene benzofuran-2 (3H) -ketone | |
| CN117417305B (en) | Synthesis method of high-purity 2- (4-methoxyphenyl) -4, 6-bis (2, 4-dihydroxyphenyl) -1,3, 5-triazine | |
| CN102952143A (en) | Preparation method of tetraphenylporphin | |
| CN110156811B (en) | Synthetic preparation method of pentaerythritol dicyclo sulfate | |
| CN101219935B (en) | Bromol production method | |
| CN102898422B (en) | Method for preparing difenoconazole | |
| EP2323990B1 (en) | Methods for the production of 2-halo-4-nitroimidazole and intermediates thereof | |
| CN102942593B (en) | Synthetic method of photoinitiator dual (2,4,6-trimethylbenzene formyl group) phenyl phosphine oxide | |
| CN115894229A (en) | A kind of selective synthesis process of monoethyl adipate | |
| CN114874080A (en) | Preparation method of 4, 4' -difluorobenzophenone | |
| CN102295605B (en) | Method for preparing benzimidazolone derivative | |
| CN113214215A (en) | Preparation method of key intermediate of olmesartan medoxomil | |
| CN105198890B (en) | A kind of production method of tetraphenylporphines | |
| CN108017586B (en) | A kind of preparation method of 5-methylpyrazine-2-carboxylic acid | |
| CN105085536A (en) | Preparation method of meso-tetraphenylchlorin | |
| CN108911944A (en) | The preparation method of 2,4 dichloro fluorobenzene | |
| KR101338297B1 (en) | One-step synthesis method of 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline | |
| CN101648912B (en) | Continuous preparation method of 4-nitro-3,5-dimethylpyridine-N-oxide | |
| CN109369357B (en) | A kind of method for preparing symmetrical diaryl ketone by catalytic oxidative carbonylation | |
| CN114920635B (en) | Preparation method of 4-hydroxy-1-indenone | |
| CN114315588B (en) | Preparation method of o-nitrobenzaldehyde |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| ASS | Succession or assignment of patent right |
Owner name: TANG JIANGTAO Free format text: FORMER OWNER: QUZHOU KEYANG CHEMICAL CO., LTD. Effective date: 20140930 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| COR | Change of bibliographic data |
Free format text: CORRECT: ADDRESS; FROM: 324012 QUZHOU, ZHEJIANG PROVINCE TO: 518000 SHENZHEN, GUANGDONG PROVINCE |
|
| TA01 | Transfer of patent application right |
Effective date of registration: 20140930 Address after: 2, unit 3, Beacon Hill garden, 201 West mud road, Shenzhen, Guangdong, Futian District 518000, China Applicant after: Tang Jiangtao Address before: 324012 A602 room, Jincheng business building, 16 labour Road, Zhejiang, Quzhou Applicant before: QUZOU KEYANG CHEMICAL Co.,Ltd. |
|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20200103 Address after: 261500 No. 5655 Kang Cheng street, Gaomi City Economic Development Zone, Weifang, Shandong Patentee after: Shandong Youyan Environmental Protection Technology Co.,Ltd. Address before: 2, unit 3, Beacon Hill garden, 201 West mud road, Shenzhen, Guangdong, Futian District 518000, China Patentee before: Tang Jiangtao |
|
| TR01 | Transfer of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20151202 Termination date: 20211108 |